Manufacture of sulphur nitride



Patented July 16, 1940 UNITED, STATES MANUFACTURE OF SULPHUR NITRIDEWillis Cunard Fernelius, Columbus, Ohio No Drawing. Application March18, 1938, Serial No. 196,627

11 Claims.

any great quantities of byproducts, a difficulty which has beenexperienced in the past.

In accordance with the invention, I bring together sulphur monochlorideor a more highly chlorinated sulphur compound and an excess of ammonia,both'reactants being substantially anhydrous, which react, in the caseof S2012, according tothe following ideal equation:

In practice, this equation merely represents the end result, which is.approached but never completely attained. Apparently the reactionproceeds through intermediate stages to a large extent, but may possiblygo directly to the end products to some extent. It is relativelyunimportant. practically, what intermediate compounds are formed solongas the end result approaches that indicated in the equation. In the pastit has been diflicult to complete the conversion of the intermediatecompounds to. the-final products.

If conditions are unfavorable, some of themtermediate products mayundergosecondary reactions, giving rise to such compounds as NzSs,SsNHz, etc. The conditions which I believe to be essential to the mostnearly complete avoidance of these undesirable by-products are excess ofNH3, and low temperature. It is highly desirable to operate innon-aqueous medium, although a small proportion of moisture, such as maybe in ordinary technical materials, can be tolerated. No extraordinarydegree of dryness is necessary. The temperature requirement is satisfiedby the preferred mode of operation to be described, but not, forexample, by bubbling NHs through equal parts-S2012 and toluene, startingat room temperature. great excess as by the employment of aliquid phasereaction wherein the S2012 or equivalent is in solution in anorganic'solvent, such as toluene,

and such solution is added to liquidammonia or I a non-aqueous liquid,such as toluene, at any convenient temperature such as room temperature,having dissolved thereinenough NHa to render the same in excess withrespect to the S2012 which is added. On account of the dilution of theS2012 by the toluene, as long as a drop orportion of solution may beconsidered as retaining its integrity in the liquid ammonia or ammoniasolution, the ammonia will be in excess at the interface. As soon as thedrop has lost its. integrity, the excess ofammonia will be even greater,but if the NH were added dropwise to the solution of I prefer to havethe ammonia present in as. by extraction with CS2 S2012, there would bean excess of NH3 at the interface so long as the drop retained itsintegrity,

' after which the S2012 would come to be present in great excess at thepoints of reaction. If ammonia were added to the S2012 solutionin; the

form of gas bubbles, S2012 would always be in ex-,

cess. 'While the addition of a solution of S2012 in toluene dropwise toliquid ammonia or a solutionof NH; in an organic solvent is the presentpreferred manner of realizing my invention, I consider that any mode ofbringing.S20l2 or equivalent compound into contact with an excess ofNHa; at a proper reaction temperature, is within the broad scopethereof. 2 v As the reaction products accumulate in the liquid ammonia,the contact between the intermediate products and the NHa becomes,poorer. Hence the need to bring the reaction to substantial completionalmost immediately by maintaining a large excess of NH3 at the points ofreaction. S014 may be used in place of S2012 as may also the so-calledS012 which has been shown to be a solution of SChand 012 in S2012.Accordingly, while S2012 is specified in the followingdescription, it isto be understood that equivalent compounds may be used.

In the preferred mode of practicing my invention, I dissolve S2012 insufiicient quantity of toluene to hold the same in solution and toreduce the intensity of the reaction to the desired degree. If thesolution is pre-cooled, it may be more concentratedr (Other organicsolvents inert to and at least partially miscible with NH3, such as0014, 01-1013, CeHs, (021-15) 20, may be used. instead of toluene.) Thissolution is cooled to a tempera ture below 33 0. and added dropwise withstirring or other form of agitation to a vessel containing an excess ofliquid ammonia. uctsof the reaction are all fairly soluble in liquidammonia so thatno precipitate is formed at the beginning of thereaction. Before precipitation has occurred to such an extent that thereaction becomes incomplete, addition of S2012 is discontinued, theammonia is removed by evaporation (preferably being recovered forreuse), toluene is removed from the residue as by filtration andevaporation, and the resulting material is leached with water to removethe NH401. The result is a free-flowing yellow-orange powder consistingsubstantially entirely of sulphur and S4N4. While the S4N4 and sulphurmay be separated and crystalliza- The prodtion from benzene, the productis useful without suchseparation, e. g., asan insecticide. Indeed,

it is superior to the pure S4N4 since the latter is explosive, while themixture is not. The sulphur,

S4N4 mixture maybe admixed with bentonite,

talc, or the like for production of a powdered insecticide, it may beused alone, or it may be dis- 29 than NH2 were evolved.

like; for exampleJ may use silica sand as a carrier i for S2012 andintroduce the same into liquid ammonia. At the end of the reaction, thesand may be separated by decantation or filtration. I may also add S2Cl2and NH3 simultaneously, with stirring, to an organic solvent, NH3 beingaddedin excess.

Example 125 cc. of S2Cl2 were dissolved in 500 cc. of toluene. Thissolution was added in discrete drops to an open vessel containing 1500cc. of liquid ammonia,with stirring. Substantially; no fumes other (Ifat any time the excess of ammonia had been destroyed, as evidenced bythe appearance of an orange or brown color instead of the customary darkpurple, liquid ammonia was added.) Upon the completion of the 1reaction, the excess of ammonia was evaporated.

The toluene was then filtered from the solids under suction. The solidwas next placed under diminished pressure until the greater part of theammonia of crystallization of the S4N4. was removed. A gradual colorchange irom a fairly bright orange to a light greenish yellow indicatedthe complete removal of ammonia. (During this operation, the mixture maybe heated to 100 C. with safety.) Following the removal of the NHs, themixture was leached with water to remove NHiC'l. When the productcontaining S4N4 and sulphur was completely air dried, it weighed 72.3 g.

To produce an insecticide suitable for use as a spray, the sulphur andsulphur nitride mixture is dissolved in a suitable quantity of asuitable solvent as above indicated. To produce an insecticide suitablefor use as a dust, the sulphur nitride mixture is thoroughly ground withseveraltimes its weight (up to 10,000) of bentonite, talc or the like.

5, 'Having thus described my invention, what I claim is:

"1. Process of making sulphur nitride comprising contacting a mixture ofasulphur chlorine compound and a non-aqueous diluent, suchsulphur-chlorine compound containing at least as many chlorine atoms assulphur atoms, with an excess of a liquidmaterial of the classconsisting of liquid NHs', and solutions of NI-ls in organic solventsboth reactants being substantially dry, N'rls being maintainedin excessin the reaction mixture at all times.

2. Process of making sulphur nitride comprising contacting a mixture ofa sulphur-chlorine com-pound with a non-aqueous diluent, suchsulphur-chlorine compound containing at-least as many chlorine atoms assulphur atoms, with an excess of a liquid material of the classconsisting of liquid NHs and solutions of NHla in organic solvents in aliquid phase reaction, both reactants being substantially dry, NHs beingmaintained in excess in the reaction mixture at all times. I 3. Processof making sulphur nitride comprising adding a solution of asulphur-chlorine compound containing at least as many chlorine atoms assulphur atoms in an organic diluent inert to liquid ammonia, in smallportions, with agitation, to a body of liquid ammonia and separating thereaction product from the .excess ammonia and theor anicdiluent; v

4. Process of making sulphur nitride comprising adding a solution of asulphur-chlorine compound containing at least as many chlorine atoms assulphur atoms in an organic diluent inert to liquid ammonia, in smallportions, with agitation, to a body of liquid ammonia, separatingthe'reaction product from the excess ammonia and the organic diluent andremoving therefrom the NH4C1 content.

5. Process of making sulphur nitride comprisingadding a solution of asulphLw-chlor-ine compound-containing at'least as many'chlo'rine' atomsas sulphur atoms in an organic solventin small portions with agitationto a body of an' organic solvent containing ammonia, separating thereaction product from the'excess ammonia and the organic solvent andremoving therefrom the -NI-I4Cl content, the concentration of am moniain the solvent-bodies being such that ammonia is always in; excess with.respect-to the I sulphur-chlorine compound.

6. Process of making sulphur nitride come prising adding a solution ofS2012 in an organic solvent inert to liquid ammonia, insmall portions,with agitation, to a body of liquid'am' monia, separatingthe reactionproduct from the excess ammoniaand the organic solvent, and removingtherefrom the m-ncl content. 1 1

'7. Process of making sulphur nitride com: prisingaddirig a solution of$2012 in an organic solvent in small portions with agitation to abody ofan organic solvent containing ammonia, separating the reaction productfrom the excess, am monia-and the organic solvent and removin therefromthe NH4C1 content, the concentration of ammonia in the solvent bodiesbeing such that respect to S2Cl2. 1

10. Process of' making sulphur nitride com prising mixing S2012 with-adiluent and contactingthe resulting mixture with liquid NHaQsaid diluentbeing present-in greater quantity than S2Cl2 and said being in excesswith'resp'ectto S2012. r- '1' 11: Process "of making sulphur nitride comprising forming amixture of a non-aqueous, in-- ert, diluent with asulphur-chlorine compound containing at least as many chlorine atoms assulphur atoms and introducing said mixture} in small. portions, into asubstance oftheclass consisting 'of liquid ammonia and inert fluidscontaining ammonia,' ammonia being maintained in 'excessinthereactionmixture.

WILLIS CPONARD FERNEuUs.

